EP4383365A2 - Matériau actif négatif pour batterie au lithium rechargeable et batterie au lithium rechargeable le comprenant - Google Patents

Matériau actif négatif pour batterie au lithium rechargeable et batterie au lithium rechargeable le comprenant Download PDF

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Publication number
EP4383365A2
EP4383365A2 EP23212718.3A EP23212718A EP4383365A2 EP 4383365 A2 EP4383365 A2 EP 4383365A2 EP 23212718 A EP23212718 A EP 23212718A EP 4383365 A2 EP4383365 A2 EP 4383365A2
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Prior art keywords
active material
negative active
lithium battery
carbon matrix
rechargeable lithium
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EP23212718.3A
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German (de)
English (en)
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EP4383365A3 (fr
EP4383365B1 (fr
Inventor
Chul Youm
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/364—Composites as mixtures
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    • C01B32/00—Carbon; Compounds thereof
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    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2002/02—Amorphous compounds
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    • C01P2002/08—Intercalated structures, i.e. with atoms or molecules intercalated in their structure
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above
    • H—ELECTRICITY
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Embodiments relate to a negative active material for a rechargeable lithium battery and a rechargeable lithium battery including the same.
  • Embodiments are directed to a negative active material for a rechargeable lithium battery, the negative active material including a porous amorphous carbon matrix having a porosity of about 10 % to about 64 %, silicon oxide distributed in pores of the porous amorphous carbon matrix, and a coating layer on a surface of the porous amorphous carbon matrix, the coating layer including an amorphous carbon.
  • the negative active material for a rechargeable lithium battery wherein the amorphous carbon matrix may include a hard carbon matrix or a soft carbon matrix.
  • the negative active material for a rechargeable lithium battery wherein the amorphous carbon matrix may include a hard carbon matrix.
  • the negative active material for a rechargeable lithium battery wherein the silicon oxide may be SiO x (where x is about 0.9 to about 2.0).
  • the negative active material for a rechargeable lithium battery wherein the porosity of the porous amorphous carbon matrix may be about 10 % to about 60 %.
  • the negative active material for a rechargeable lithium battery wherein the silicon oxide may have a particle diameter of about 1 nm to about 100 nm.
  • the negative active material for a rechargeable lithium battery wherein an amount of the silicon oxide may be about 10 wt% to about 60 wt% based on 100 wt% of the negative active material.
  • the negative active material for a rechargeable lithium battery wherein an amount of the coating layer may be about 1 wt% to about 20 wt% based on 100 wt% of the negative active material.
  • the negative active material for a rechargeable lithium battery wherein the amorphous carbon in the coating layer may include soft carbon.
  • the negative active material for a rechargeable lithium battery wherein the silicon oxide may be amorphous silicon oxide.
  • Embodiments are directed to a method of preparing a negative active material for a rechargeable lithium battery, the method including adding a porous amorphous carbon matrix having a porosity of about 10 % to about 64 % to a liquid silane compound to prepare a mixture, defoaming the mixture to prepare a defoamed product, mixing the defoamed product with an amorphous carbon precursor to prepare a mixed product, and heat-treating the mixed product.
  • the method of preparing a negative active material for a rechargeable lithium wherein the porosity of the porous amorphous carbon matrix may be about 10 % to about 60 %.
  • the method of preparing a negative active material for a rechargeable lithium wherein the amorphous carbon matrix may include a hard carbon matrix or a soft carbon matrix.
  • the method of preparing a negative active material for a rechargeable lithium battery wherein the silane compound may include tetraalkyl orthosilicate, tetraalkoxysilane, silicon tetrachloride, or combinations thereof.
  • the method of preparing a negative active material for a rechargeable lithium battery wherein the heat-treatment may be performed at about 600 °C to about 1,000 °C.
  • the method of preparing a negative active material for a rechargeable lithium battery wherein the defoamed product may be distributed in a solvent before being mixed with the amorphous carbon precursor.
  • the method of preparing a negative active material for a rechargeable lithium battery wherein the solvent may include water.
  • a rechargeable lithium battery which includes a negative electrode including the negative active material, a positive electrode, and an electrolyte.
  • soft carbon refers to graphitizable carbon materials and are readily graphitized by heat treatment at a high temperature, e.g., 2800 °C
  • hard carbon refers to non-graphitizable carbon materials and are slightly graphitized by heat treatment.
  • a negative active material for a rechargeable lithium battery may include a porous amorphous carbon matrix having a porosity of about 10 % to about 64 % and a coating layer on a surface of the matrix.
  • the coating layer may include an amorphous carbon and the pores of amorphous carbon matrix may include silicon oxide therein.
  • the negative active material 1 includes the porous amorphous carbon matrix 3, silicon oxide 5 distributed in the pores, and a coating layer 7 including an amorphous carbon.
  • the amorphous carbon matrix may be a hard carbon matrix or a soft carbon matrix. According to some embodiments, the amorphous carbon matrix may be the hard carbon matrix.
  • the silicon oxide may be SiO x , where x is about 0.9 to about 2.0 (e.g. SiO 2 ).
  • silicon oxide may be present in the pores of the amorphous carbon, e.g., in a hard carbon matrix or a soft carbon matrix. Because hard and soft carbon matrices rarely expand during charging and discharging, the amorphous carbon matrix may physically suppress the volume expansion of silicon during charging and discharging. This may improve the cycle-life characteristics of the silicon-based negative active material.
  • the volume suppression effect of the carbon matrix may be realized by using either a hard carbon matrix or a soft carbon matrix. The effect may not be sufficiently obtained by using a crystalline carbon such as graphite.
  • the silicon oxide may have a particle diameter (e.g. an average particle diameter, such as D50) of about 1 nm to about 100 nm, about 2 nm to about 90 nm, or about 3 nm to about 50 nm. If the particle diameter of silicon oxide is within these ranges, stress on the amorphous carbon matrix due to the volume expansion of the active material may be dispersed. The volume suppression effect of the porous hard carbon matrix or porous soft carbon matrix may thereby be improved.
  • a particle diameter e.g. an average particle diameter, such as D50
  • the porous amorphous carbon matrix may include at least one pore and may have a porosity of about 10 % to about 64%, about 10 % to about 60 %, about 10% to about 50%, about 20% to about 50%, about 30% to about 50%, or about 40% to about 50%. If the porosity of the porous amorphous carbon matrix is within these ranges, the silicon oxide may be sufficiently stored in the pores and the matrix form of the amorphous carbon may be maintained during charge and discharge, and thus, excellent capacity, charge and discharge efficiency, and cycle-life characteristics may be exhibited. In some embodiments, the porosity may be measured by a BJH method using a nitrogen adsorption method.
  • an amount of the silicon oxide may be about 10 wt% to about 60 wt%, about 20 wt% to about 55 wt%, or about 30 wt% to about 50 wt% based on 100 wt% of the negative active material. If the amount of silicon oxide is within these ranges, the porous amorphous carbon matrix may be well maintained without increases in the irreversible capacity, the volume expansion of the active material may be suppressed, and charge and discharge capacity may be increased.
  • An amount of the coating layer may be about 1 wt% to about 20 wt%, about 2 wt% to about 15 wt%, or about 3 wt% to about 10 wt% based on 100 wt% of the negative active material. If the amount of coating layer is within these ranges, the improved conductivity, as a result of the coating layer, may be effectively obtained without a decrease in charge and discharge capacity or an increase in resistance.
  • the silicon oxide may be amorphous.
  • the inclusion of amorphous silicon oxide in the negative active material may prevent the structure from breaking, despite repeated charging and discharging, resulting in improved cycle-life characteristics.
  • the amorphous carbon included in the coating layer may be soft carbon.
  • Such a negative active material according to one or more embodiments may be prepared by the following procedures.
  • a porous amorphous carbon matrix including at least one pore may be added to a liquid silane compound to prepare a mixture.
  • the amorphous carbon matrix may be a hard carbon matrix or a soft carbon matrix. According to some embodiments, the amorphous carbon matrix may be the hard carbon matrix.
  • the porous amorphous carbon matrix may have a porosity of about 10 % to about 64 %, about 10 % to about 60 %, about 10 % to about 50 %, about 20% to about 50%, about 30% to about 50%, or about 40% to about 50%.
  • the addition may be performed by distributing the porous amorphous carbon matrix in the liquid silane compound.
  • a mixing ratio of the porous amorphous carbon matrix and the liquid silane compound may be appropriately adjusted depending on the porosity of the porous amorphous carbon matrix, e.g., the mixing ratio may be appropriately adjusted so that there is sufficient liquid silane compound to fill the pores of the porous amorphous carbon matrix.
  • the amorphous silicon oxide may penetrate the pores of the porous amorphous carbon matrix in a suitable amount. If a vapor-type silane compound is used, the pores of the porous amorphous carbon matrix may be blocked, and the silane compound may be undesirably deposited on a surface of the porous amorphous carbon matrix. If a pulverized solid-type silane compound is used, the silane may be unable to penetrate the pores of the porous amorphous carbon matrix, and the volume expansion of the silane compound during charge and discharge may not be physically constrained by the porous amorphous carbon matrix.
  • the silane compound may be tetraalkyl orthosilicate, tetraalkoxysilane, silicon tetrachloride, or combinations thereof.
  • the tetraalkyl orthosilicate may be tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, or combinations thereof (e.g. tetramethyl orthosilicate, tetraethyl orthosilicate, or combinations thereof).
  • the tetraalkoxy silane may be tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, or combinations thereof.
  • the mixture may be defoamed in order to prepare a defoamed product.
  • the defoaming may be performed by a vacuum reduced pressure process.
  • the defoaming may remove air from the pores of the matrix, allowing the liquid silane compound to penetrate into the pores.
  • the defoaming may be performed under a vacuum condition.
  • the pressure of the vacuum condition may be about 10 -3 MPa to about 10 -6 MPa. If the vacuum condition is within this pressure range, air in the pores may be sufficiently removed, thereby allowing the liquid silane compound to substantially and sufficiently penetrate the pores of the amorphous carbon matrix.
  • the resulting defoamed product may be mixed with an amorphous carbon precursor.
  • a mixing ratio of the defoamed product and the amorphous carbon precursor may range from about 80:20 to 99:1 by weight ratio.
  • a mixing ratio of the defoamed product and the amorphous carbon within this range may ensure that the amorphous carbon is not included in the final negative active material in an excessive amount, and thus, may enable more suitable utilization of silicon, which leads to exhibition of excellent initial efficiency.
  • the amorphous carbon precursor may include coal pitch, petroleum pitch, mesophase pitch, meso carbon pitch, coal-based oil, petroleum-based heavy oil, tar, coal-based cokes, petroleum-based cokes, green cokes, low-molecular weight heavy oil, or a polymer resin such as a phenol resin, a furan resin, a polyimide resin, or the like.
  • the amorphous carbon precursor may include coal pitch, petroleum pitch, mesophase pitch, tar, coal-based cokes, petroleum-based cokes, green cokes, low-molecular weight heavy oil, or combinations thereof which may be used for preparing soft carbon.
  • the defoamed product may be dispersed in a solvent.
  • the solvent may include water. If the defoamed product is dispersed in a solvent, e.g., water, a coupling reaction may occur and the silane compound may be converted into SiO x . Because it is difficult for water to completely penetrate the hard carbon matrix, silane compound present in a central portion of the hard carbon matrix may not be converted into SiO x . If the defoamed product is dispersed in a solvent, a filtration and a drying may be further performed.
  • the obtained product may be heat-treated.
  • the heat-treatment may be performed at about 600 °C to about 1,000 °C (e.g. about 600 °C to about 800 °C, or about 600 °C to about 700 °C).
  • the heat-treatment may be performed under an atmosphere of an argon, nitrogen, or combinations thereof.
  • the heat-treatment may be performed for about 3 hours to about 9 hours (e.g. about 4 hours to about 8 hours, or about 5 hours to about 7 hours).
  • the heat-treatment may allow the silane compound to link as a polymer, e.g., the coupling reaction may completely occur, and the silane compound in the pores of the amorphous carbon matrix may be completely converted into SiO x and may be positioned as silicon oxide in the pores.
  • the amorphous carbon precursor may be converted into the amorphous carbon which may be positioned as a coating layer surrounding a surface of the carbon matrix.
  • a rechargeable lithium battery including a negative electrode, a positive electrode, and an electrolyte.
  • the negative electrode may include a current collector and a negative active material layer formed on the current collector and including the negative active material according to embodiments.
  • the negative active material layer may include the negative active material according to some embodiments as a first negative active material and crystalline carbon as a second negative active material.
  • a mixing ratio of the first negative active material and the second negative active material may be a weight ratio of about 1:99 to about 50:50.
  • the negative active material may include the first negative active material and the second negative active material at a weight ratio of about 5:95 to about 20:80.
  • an amount of the negative active material may be about 95 wt% to about 98 wt% based on the total 100 wt% of the negative active material layer.
  • the negative active material layer may include a binder, and may further include a conductive material.
  • the amount of the binder may be about 1 wt% to about 5 wt% based on the total 100 wt% of the negative active material layer.
  • the amount of the conductive material may be about 1 wt% to about 5 wt% based on the total 100 wt% of the negative active material layer.
  • the binder may improve binding properties of negative active material particles with one another as well as with a current collector.
  • the binder may be a non-aqueous binder, an aqueous binder, or a combination thereof.
  • the non-aqueous binder may be an ethylene propylene copolymer, polyacrylonitrile, polystyrene, polyvinylchloride, carboxylated polyvinylchloride, polyvinyl fluoride, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamide imide, polyimide, or combinations thereof.
  • the aqueous binder may be a styrene-butadiene rubber (SBR), an acrylated styrene-butadiene rubber (ABR), an acrylonitrile-butadiene rubber, an acrylic rubber, a butyl rubber, a fluorine rubber, an ethylene oxide-containing polymer, polyvinyl pyrrolidone, polypropylene, polyepichlorohydrin, polyphosphazene, an ethylene propylene diene copolymer, polyvinyl pyridine, chlorosulfonated polyethylene, latex, polyester resin, an acrylic resin, a phenolic resin, an epoxy resin, polyvinyl alcohol, or combinations thereof.
  • SBR styrene-butadiene rubber
  • ABR acrylated styrene-butadiene rubber
  • ABR acrylonitrile-butadiene rubber
  • acrylic rubber a butyl rubber
  • a fluorine rubber an ethylene oxide
  • a cellulose-based compound may be further used to provide viscosity as a thickener.
  • the cellulose-based compound may include one or more of carboxymethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, or alkali metal salts thereof.
  • the alkali metal may be Na, K, or Li.
  • the thickener may be included in an amount of about 0.1 parts by weight to about 3 parts by weight based on 100 parts by weight of the negative active material.
  • the conductive material may provide electrode conductivity, and any electrically conductive material may be used as a conductive material unless it causes a chemical change.
  • the conductive material may be, e.g., a carbon-based material such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, a carbon fiber, and the like; a metal-based material of a metal powder or a metal fiber including copper, nickel, aluminium, silver, and the like; a conductive polymer such as a polyphenylene derivative; or a mixture thereof.
  • the current collector may include, e.g., a copper foil, a nickel foil, a stainless steel foil, a titanium foil, a nickel foam, a copper foam, a polymer substrate coated with a conductive metal, and a combination thereof, but is not limited thereto.
  • the positive electrode may include a current collector and a positive active material layer formed on the current collector.
  • the positive electrode active material may include lithiated intercalation compounds that reversibly intercalate and deintercalate lithium ions.
  • one or more composite oxides of a metal selected from cobalt, manganese, nickel, and a combination thereof, and lithium, may be used.
  • the compounds represented by one of the following chemical formulae may be used.
  • Li a A 1-b X b D 1 2 (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5); Li a A 1-b X b O 2-c1 D 1 c1 (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c1 ⁇ 0.05); Li a E 1-b X b O 2-c1 D 1 c1 (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c1 ⁇ 0.05); Li a E 2-b X b O 4-c1 D 1 c1 (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c1 ⁇ 0.05); Li a Ni 1-b-c Co b X c D 1 ⁇ (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.5, 0 ⁇ 2); Li a Ni 1-b-c Co b X c O 2- ⁇ T ⁇ (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.5, 0 ⁇ 2); Li a Ni 1-b
  • A is selected from Ni, Co, Mn, or combinations thereof;
  • X is selected from Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, and combinations thereof;
  • D 1 is selected from O, F, S, P, or combinations thereof;
  • E is selected from Co, Mn, or combinations thereof;
  • T is selected from F, S, P, or combinations thereof;
  • G is selected from Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or combinations thereof;
  • Q is selected from Ti, Mo, Mn, or combinations thereof;
  • Z is selected from Cr, V, Fe, Sc, Y, or combinations thereof;
  • J is selected from V, Cr, Mn, Co, Ni, Cu, or combinations thereof;
  • L 1 is selected from Mn, Al, or combinations thereof.
  • the compounds may have a coating layer on the surface, or may be mixed with another compound having a coating layer.
  • the coating layer may include at least one coating element compound selected from the group consisting of an oxide of a coating element, a hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, and a hydroxyl carbonate of a coating element.
  • the compound for the coating layer may be amorphous or crystalline.
  • the coating element included in the coating layer may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof.
  • the coating layer may be disposed in a method having no adverse influence on properties of a positive electrode active material by using these elements in the compound, and for example, the method may include any coating method such as spray coating, dipping, and the like, but is not illustrated in more detail since it is well-known in the related field.
  • an amount of the positive active material may be about 90 wt% to about 98 wt% based on the total weight of the positive active material layer.
  • the positive active material layer may further include a binder and a conductive material.
  • the binder and the conductive material may be included in an amount of about 1 wt% to about 5 wt%, respectively based on the total amount of the positive active material layer.
  • the binder may improve the binding properties of positive active material particles with one another as well as with a current collector.
  • the binder may be, e.g., polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinylchloride, carboxylated polyvinylchloride, polyvinyl fluoride, an ethylene oxide-containing polymer, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, a styrene butadiene rubber, an acrylated styrene butadiene rubber, an epoxy resin, nylon, and the like, but are not limited thereto.
  • the conductive material is included to provide electrode conductivity, and any electrically conductive material may be used as a conductive material unless it causes a chemical change.
  • the conductive material may include a carbon-based material such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, a carbon fiber and the like; a metal-based material of a metal powder or a metal fiber including copper, nickel, aluminium, silver, and the like; a conductive polymer such as a polyphenylene derivative; or a mixture thereof.
  • the current collector may include Al, but is not limited thereto.
  • the electrolyte may include a non-aqueous organic solvent and a lithium salt.
  • the non-aqueous organic solvent serves as a medium for transmitting ions taking part in the electrochemical reaction of a battery.
  • the non-aqueous organic solvent may include a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, or aprotic solvent.
  • the carbonate-based solvent may include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), or the like.
  • the ester-based solvent may include methyl acetate, ethyl acetate, n-propyl acetate, dibutyl acetate, methyl propionate, ethyl propionate, decanolide, mevalonolactone, caprolactone, or the like.
  • the ether-based solvent may include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, or the like.
  • the ketone-based solvent may include cyclohexanone, or the like.
  • the alcohol-based solvent may include ethyl alcohol, isopropyl alcohol, and the like, and examples of the aprotic solvent include nitriles such as R-CN (where R is a C2 to C20 linear, branched, or cyclic hydrocarbon, and may include a double bond, an aromatic ring, or an ether bond), amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolanes, and the like.
  • R-CN where R is a C2 to C20 linear, branched, or cyclic hydrocarbon, and may include a double bond, an aromatic ring, or an ether bond
  • amides such as dimethylformamide
  • dioxolanes such as 1,3-dioxolane
  • sulfolanes and the like.
  • the organic solvent may be used alone or in a mixture. If the organic solvent is used in a mixture, the mixture ratio may be controlled in accordance with a desirable battery performance, and it may be well known to those skilled in the related art.
  • the carbonate-based solvent may desirably include a mixture with a cyclic carbonate and a linear carbonate.
  • the cyclic carbonate and linear carbonate are mixed together in a volume ratio of about 1:1 to about 1:9, and if the mixture is used as an electrolyte, it may have enhanced performance.
  • the organic solvent may further include an aromatic hydrocarbon-based solvent as well as the carbonate-based solvent.
  • the carbonate-based solvent and the aromatic hydrocarbon-based solvent may be mixed together in a volume ratio of about 1:1 to about 30:1.
  • the aromatic hydrocarbon-based organic solvent may be an aromatic hydrocarbon-based compound represented by Chemical Formula 1.
  • R 1 to R 6 may be the same or different and may each be selected from hydrogen, a halogen, a C1 to C10 alkyl group, a haloalkyl group, or a combination thereof.
  • aromatic hydrocarbon-based organic solvent may be selected from benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4-triiodobenzene, toluene, fluorotoluene, 2,3-difluorotoluene, 2,4-di
  • the electrolyte may further include vinylethyl carbonate, vinylene carbonate, an ethylene carbonate-based compound represented by Chemical Formula 2 as an additive for improving cycle life.
  • R 7 and R 8 may be the same or different and may each be independently hydrogen, a halogen, a cyano group (CN), a nitro group (NO 2 ), or a C1 to C5 fluoroalkyl group, provided that at least one of R 7 and R 8 is a halogen, a cyano group (CN), a nitro group (NO 2 ), or a C1 to C5 fluoroalkyl group, and R 7 and R 8 are not simultaneously hydrogen.
  • Examples of the ethylene carbonate-based compound may be difluoro ethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate, fluoroethylene carbonate, or the like.
  • An amount of the additive for improving the cycle-life characteristics may be used within an appropriate range.
  • the lithium salt dissolved in an organic solvent supplies a battery with lithium ions, basically operates the rechargeable lithium battery, and improves transportation of the lithium ions between a positive electrode and a negative electrode.
  • the lithium salt include at least one or two supporting salts selected from LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN(SO 2 C 2 F 5 ) 2 , Li(CF 3 SO 2 ) 2 N, LiN(SO 3 C 2 F 5 ) 2 , Li(FSO 2 ) 2 N (lithium bis(fluorosulfonyl)imide: LiFSI), LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiPO 2 F 2 , LiN (C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ), wherein x and y are natural numbers, e.g., an integer of about 1 to about 20, lithium difluoro(bisoxal
  • a separator may be between the positive electrode and the negative electrode depending on a type of a rechargeable lithium battery.
  • the separator may use polyethylene, polypropylene, polyvinylidene fluoride or multi-layers thereof having two or more layers and may be a mixed multilayer such as a polyethylene/polypropylene double-layered separator, a polyethylene/polypropylene/polyethylene triple-layered separator, a polypropylene/polyethylene/polypropylene triple-layered separator, and the like.
  • FIG. 2 is an exploded perspective view of a rechargeable lithium battery according to an embodiment.
  • the rechargeable lithium battery according to some embodiments is illustrated as a prismatic battery but may include variously-shaped batteries such as a cylindrical battery, a pouch battery, and the like.
  • a rechargeable lithium battery 100 may include an electrode assembly 40 manufactured by winding a separator 30 disposed between a positive electrode 10 and a negative electrode 20 and a case 50 housing the electrode assembly 40.
  • An electrolyte may be impregnated in the positive electrode 10, the negative electrode 20 and the separator 30.
  • a porous hard carbon matrix (porosity: 10%) was added to a liquid tetraethyl orthosilicate (TEOS) to prepare a mixture.
  • TEOS liquid tetraethyl orthosilicate
  • the mixture was defoamed by vacuum reducing pressure of 10 -6 MPa pressure.
  • the defoamed product was distributed in water.
  • the obtained product and meso pitch were mixed at a weight ratio of 90:10, and the resulting mixture was heat-treated at 600 °C for 5 hours under a N 2 atmosphere to prepare a negative active material.
  • the prepared negative active material had a porous hard carbon matrix, silicon oxide (SiO x , where x is 2) positioned in the pores of the hard carbon matrix, and a soft carbon coating layer on a surface of the hard carbon matrix.
  • An amount of the hard carbon matrix was 81 wt%, an amount of the silicon oxide was 9 wt%, and an amount of the soft carbon coating layer was 10 wt%.
  • the silicon oxide had a particle diameter of 5 nm.
  • the negative active material slurry was coated on a Cu foil current collector, dried, and pressurized to prepare a negative electrode including the current collector and a negative active material layer formed on the current collector.
  • a rechargeable lithium cell was fabricated.
  • the electrolyte 1M LiPF 6 dissolved in a mixed solvent of ethylene carbonate and dimethyl carbonate (3:7 volume ratio) was used.
  • a negative active material was prepared by the same procedure as in Example 1, except that a porous hard carbon matrix with a porosity of 50 % was used.
  • the prepared negative active material had a porous hard carbon matrix, silicon oxide (SiO x , where x is 2) positioned in the pores of the hard carbon matrix, and a soft carbon coating layer on a surface of the hard carbon matrix.
  • An amount of the hard carbon matrix was 45 wt%
  • an amount of the silicon oxide was 45 wt%
  • an amount of the soft carbon coating layer was 10 wt%.
  • the silicon oxide had a particle diameter of 5 nm.
  • the negative active material was used to fabricate a negative electrode and a half-cell by the same procedure as in Example 1.
  • a negative active material was prepared by the same procedure as in Example 1, except that a porous hard carbon matrix with a porosity of 60 % was used.
  • the prepared negative active material had a porous hard carbon matrix, silicon oxide (SiO x , where x is 2) positioned in the pores of the hard carbon matrix, and a soft carbon coating layer on a surface of the hard carbon matrix.
  • An amount of the hard carbon matrix was 36 wt%, an amount of the silicon oxide was 54 wt%, and an amount of the soft carbon coating layer was 10 wt%.
  • the silicon oxide had a particle diameter of 5 nm.
  • the negative active material was used to fabricate a negative electrode and a half-cell by the same procedure as in Example 1.
  • a negative active material was prepared by the same procedure as in Example 1, except that a porous soft carbon matrix with a porosity of 50 % was used.
  • the prepared negative active material had a porous soft carbon matrix, silicon oxide (SiO x , where x is 2) positioned in the pores of the soft carbon matrix, and a soft carbon coating layer on a surface of the soft carbon matrix.
  • An amount of the soft carbon matrix was 45 wt%
  • an amount of the silicon oxide was 45 wt%
  • an amount of the soft carbon coating layer was 10 wt%.
  • the silicon oxide had a particle diameter of 5 nm.
  • the negative active material was used to fabricate a negative electrode and a half-cell by the same procedure as in Example 1.
  • a negative active material was prepared by the same procedure as in Example 1, except that a porous hard carbon matrix with a porosity of 50 % and liquid tetramethylorthosilicate (TMOS) were used.
  • the prepared negative active material had a porous hard carbon matrix, silicon oxide (SiO x , where x is 2) positioned in the pores of the hard carbon matrix, and a soft carbon coating layer on a surface of the hard carbon matrix.
  • An amount of the hard carbon matrix was 45 wt%
  • an amount of the silicon oxide was 45 wt%
  • an amount of the soft carbon coating layer was 10 wt%.
  • the silicon oxide had a particle diameter of 5 nm.
  • the negative active material was used to fabricate a negative electrode and a half-cell by the same procedure as in Example 1.
  • a negative active material was prepared by the same procedure as in Example 2, except that the obtained product and meso pitch were mixed at a weight ratio of 99:1.
  • the prepared negative active material had a porous hard carbon matrix, silicon oxide (SiO x , where x is 2) positioned in the pores of the hard carbon matrix, and a soft carbon coating layer on a surface of the hard carbon matrix.
  • An amount of the hard carbon matrix was 49.5 wt%
  • an amount of the silicon oxide was 49.5 wt%
  • an amount of the soft carbon coating layer was 1 wt%.
  • the silicon oxide had a particle diameter of 5 nm.
  • the negative active material was used to fabricate a negative electrode and a half-cell by the same procedure as in Example 1.
  • a negative active material was prepared by the same procedure as in Example 2, except that the obtained product and meso pitch were mixed at a weight ratio of 80:20.
  • the prepared negative active material had a porous hard carbon matrix, silicon oxide (SiO x , where x is 2) positioned in the pores of the hard carbon matrix, and a soft carbon coating layer on a surface of the hard carbon matrix.
  • An amount of the hard carbon matrix was 40 wt%
  • an amount of the silicon oxide was 40 wt%
  • an amount of the soft carbon coating layer was 20 wt%.
  • the silicon oxide had a particle diameter of 5 nm.
  • the negative active material was used to fabricate a negative electrode and a half-cell by the same procedure as in Example 1.
  • a negative active material was prepared by the same procedure as in Example 1, except that a porous hard carbon matrix with a porosity of 65 % was used.
  • the prepared negative active material had a porous hard carbon matrix, silicon oxide (SiO x , where x is 2) positioned in the pores of the hard carbon matrix, and a soft carbon coating layer on a surface of the hard carbon matrix.
  • An amount of the hard carbon matrix was 31.5 wt%, an amount of the silicon oxide was 58.5 wt%, and an amount of the soft carbon coating layer was 10 wt%.
  • the silicon oxide had a particle diameter of 5 nm.
  • the negative active material was used to fabricate a negative electrode and a half-cell by the same procedure as in Example 1.
  • a negative active material was prepared by the same procedure as in Example 1, except that a porous hard carbon matrix with a porosity of 5 % was used.
  • the prepared negative active material had a porous hard carbon matrix, silicon oxide (SiO x , where x is 2) positioned in the pores of the hard carbon matrix, and a soft carbon coating layer on a surface of the hard carbon matrix.
  • An amount of the hard carbon matrix was 85.5 wt%, an amount of the silicon oxide was 4.5 wt%, and an amount of the soft carbon coating layer was 10 wt%.
  • the silicon oxide had a particle diameter of 5 nm.
  • the negative active material was used to fabricate a negative electrode and a half-cell by the same procedure as in Example 1.
  • a porous hard carbon matrix (porosity: 50%) was added to a liquid tetraethyl orthosilicate (TEOS) to prepare a mixture.
  • TEOS liquid tetraethyl orthosilicate
  • the mixture was defoamed by vacuum reducing pressure of 10 -6 MPa pressure.
  • the defoamed product was heat-treated at 600 °C for 5 hours under a N 2 atmosphere to prepare a negative active material.
  • the prepared negative active material had a porous hard carbon matrix and silicon oxide (SiO x , where x is 2) positioned in the pores of the hard carbon matrix.
  • An amount of the hard carbon matrix was 50 wt%, an amount of the silicon oxide was 50 wt%.
  • the silicon oxide had a particle diameter of 5 nm.
  • the negative active material was used to fabricate a negative electrode and a half-cell by the same procedure as in Example 1.
  • Example 1 Porosity of matrix (%) Type of silane compound Amount of amorphous carbon coating layer (wt%) Capacity (mAh/g) Efficienc y (%) Capacity retention (%)
  • Example 2 50 TEOS 10 1216 82 79 Example 3 60 TEOS 10 1393 79 77
  • Example 4 50 TEOS 10 1223 83
  • Example 5 50 TMOS 10 1309 81
  • Example 6 50 TEOS 1 1233 81
  • Example 7 50 TEOS 20 1201
  • Comparative Example 2 5 TEOS 10 334 84 84 Comparative Example 3 50 TEOS 0 1238 80 33
  • Examples 1 to 7 using the negative active material including the porous carbon matrix with a porosity of 10 % to 60 % and an amorphous carbon coating layer exhibited excellent capacity, efficiency, and cycle-life characteristics.
  • Comparative Example 3 including the negative active material with no amorphous carbon coating layer exhibited significantly deteriorated cycle-life characteristics.
  • the term "combination thereof' may include a mixture, a laminate, a complex, a copolymer, an alloy, a blend, a reactant of constituents.
  • a particle diameter or size may indicate an average particle diameter.
  • the average particle diameter indicates an average particle diameter (D50) where a cumulative volume is about 50 volume% in a particle size distribution.
  • the average particle size (D50) may be measured by a method well known to those skilled in the art, for example, by a particle size analyzer, or by a transmission electron microscopic image, or a scanning electron microscopic image.
  • a dynamic light-scattering measurement device is used to perform a data analysis, and the number of particles is counted for each particle size range, and from this, the average particle diameter (D50) value may be easily obtained through a calculation.
  • a crystalline carbon such as graphite
  • a crystalline carbon negative active material is used as a negative active material in rechargeable lithium batteries.
  • higher energy density can be, even theoretically, obtained from a crystalline carbon negative active material.
  • silicon-based active material is being conducted.
  • Silicon however, has lower initial efficiency than crystalline carbon and worse cycle-life characteristics due to large changes in volume during charge and discharge. Thus, at this time, silicon-based active materials are limited in use.
  • Some embodiments provide a negative active material for a rechargeable lithium battery exhibiting excellent cycle-life characteristics.
  • Another embodiment provides a rechargeable lithium battery including the negative active material.

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EP23212718.3A 2022-12-06 2023-11-28 Matériau actif négatif pour batterie au lithium rechargeable et batterie au lithium rechargeable le comprenant Active EP4383365B1 (fr)

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